Polyazo dyestuffs



United States Patent Q POLYAZO DYESTUFFS Hans Ischer, Ernst Iselin, and Walter Wehrli, Basel, Switzerland, assignors to Sandoz A. G., Basel, Switzerland, a Swiss firm No Drawing. Application March 27 1953, Serial N0. 345,262

Claims priority, application Switzerland November 27, 1952 5 Claims. (Cl. 260-145) The present invention relates to polyazo dyestuffs.

In accordance with this invention, a group of valuable polyazo dyestuffs is obtained by coupling one mol of the diazo compound from an aminodisazo dyestuff of the formula OCH:

wherein each of A and B represents a radical of the benzene or naphthalene series, the two N=N- groups are in para-position with respect to each other, and nucleus I may be further substituted by methyl, methoxy or acylamino, with one mol of the copper complex compound of a monoazo dyestutf of the formula ing component A, for example 1-aminobenzene-2,5-disulfonic acid, coupling the resultant diazo compound in weakly acid medium with a middle component B, for example l-amino-3-methylbenzene, further diazotizing the thus-obtained monoazo dyestuflf, and coupling the diazotized product with a component capable of metal complex formation, for example 4-methyl-1-methoxy- 2-aminobenzene, in weakly acid medium.

However, the aminodisazo dyestuffs corresponding to the aforesaid formula (a) may also be produced by coupling for example, the diazo compound of 1-amino-4-nitrobenzene-Z-sulfonic acid in alkaline medium with a lhydroxybenzene-Z-carboxylic acid, reducing the nitro group of the resultant monoazo dyestuif by means of sodium sulfide, then further diazotizing and coupling the thus-diazotized product with a middle component capable of metal complex formation, such for example as 1-methoxy-2-amino-4-acetylaminobenzene, in weakly acid medium.

Illustrative of starting or initial components A for the preparation of the said aminodisazo dyestufis are inter alia: aminobenzene, 1-amino-2methylbenzene, l-amino S-methylbenzene, 1-amino-4-methylbenzene, l-amino-2,3-

2,737,510 Patented Mar. 6, 1956 ICE dimethylbenzene, 1-amino-2,4-dimethylbenzene, l-amino- 2,5-dimethylbenzene, 1-amino-2,6-dimethylbenzene, 1- aminobenzene-Z-sulfonic acid, 1-aminobenzene-3-sulfonic acid, 1-aminobenzene-4-sulfonic acid, l-aminobenzene- 2,4-disu1fonic acid, l-aminobenzene-2,S-disulfonic acid, l-amino-2-methylbenzene-4-sulfonic acid, l-amino 2- methylbenzene-S-sulfonic acid, l-amino-4,6-dimethy1- benzene-Z-sulfonic acid, l-aminobenzene-2-carboxylic acid, 1-aminobenzene-3-carboxylic acid, l-aminobenzene- 4-carboxylic acid, l-amino-4-hydroxybenzene-3-carboxylic acid, 1 amino 3 hydroxybenzene 4 carboxylic acid, 1-amino-3-methyl-4-hydroxybenzene-S-carboxylic acid, l-amino-4-hydroxy-5-carboxybenzene-3-sulfonic acid, 1-amino-4-acetylaminobenzene-Z-sulfonic acid, as well as other aminobenzenes substituted by SOaI-I, COOI-I, halogen, -OH, alkoxy and/or alkyl groups; also l-aminonaphthalene, Z-aminonaphthalene, Z-aminonaphthalene-.3-carboxylic acid, l-aminonaphthalene-4-sulfonic acid, 1-aminonaphthalene-5-sulfonic acid, l-aminonaphthalene-S-sulfonic acid, 1-aminonaphthalene-3,6-disnlfonic acid, 1-aminonaphtha'l'ene-4,8-disulfonic acid, 1- aminonaphthalene-3,8-disulfonic acid, Z-aminonaphthalene-l-sulfonic acid, 2-aminonaphthalene-6-sulfonic acid, 2-aminonaphthalene-8-sulfonic acid, Z-aminonaphthalene- 4,8-disulfonic, acid, 2-aminonaphthalene-S,7-disulfonic acid, 2-aminonaphthalene-6,8-disulfonic acid, 2-aminonaphthalene-3,6-disulfonic acid, 1-aminonaphthalene-3,6, 8-trisulfonic acid, as well as other aminonaphthalene sulfonic acids.

Illustrative of middle components B are inter alia: aminobenzene, 1 amino-3-methylbenzene, 1-amino-2,5- dimethylbenzene, 1 amino-2-methoxybenzene, l-amino- 3-methoxybenzene, 1-amino-2-methyl-5-methoxybenzene, 1-amino-2,5-dimethoxybenzene, l-amino 2,5-diethoxybenzene, 1-amino-3-acetylaminobenzene, 1 amino 2- methoxy-S-acetylaminobenzene, l-aminonaphthalene, 1- aminonaphthalene-6sulfonic acid, 1-aminonaphthalene-7- sulfonic acid, 1-amino-Z-methoxynaphthalene, l-amino-Z- ethoxynaphthalene, l-amino 2 mcthylnaphthalene, 1- amino-Z-methoxynaphthalene-6-sulfonic acid, l-amino-Z- ethoxynaphthalene-6-sulfonic acid, etc. Instead of a monoazo dyestufi from an initial component A and a middle component B, it is also possible to use for example 4-amino-1,1'-azobenzene, 4-amino-1,l-azobenzene-4'-sulformylaminobenzene, l amino-Z-methoxy-S-benzoylaminobenzene, 1-amino2-methoxy-5 cinnamoylaminobene, etc.

Illustrative of amines of nucleus I are inter alia: 1- amino-2-methoxybenzene, l-amino-Z-methoxy-S-methylbenzene, l-amino-2,5-dimethoxybenzene, 1 amino 2- methoxy-S-acetylaminobenzene, l-amino 2-rnethoxy-5- formylaminobenzene, l-amino-Z-methoxy 5 benzoylaminobenzene, l-amino-Z-methoxy 5 cinnamoylaminobenzene, etc.

In the monoazo dyestuffs of formula (b), the symbol R preferably stands e. g. for a radical of l-hydroxynaphthalene-3-sulfonic acid, 1-hydroxynaphthalene-4-sulfonic acid, 1-hydroxynaphthalene-S-sulfonic acid, 2-hydroxynaphthalene-4-sulfonic acid, Z-hydroxynaphthalene- 6-sulfonic acid, 2-hydroxynaphthalene-7-sulfonic acid, 1- hydroxynaphthalene-3,6-disulfonic acid, l-hydroxynaphthalene-3,8-disulfonic acid, l-hydroxynaphthalene-4,8-disulfonic acid, 2-hydroxynaphthalene-3,6-disu1fonic acid, 2-hydroxynaphthalene-6,8-disulfonic acid, 1 hydroxynaphthalene-3,5,7-trisulfonic acid, l-hydroxynaphthalene- 3,6,8-trisulfonic acid, l-phenyl-3-methyl-5-pyrazolone, 1- phenyl-3-methyl-5-pyrazolone-2'-sulfonic acid, l-phenyl- 3-methyl-5-pyrazolone-3'-sulfonic acid, 1 phenyl 3- methyl 5 pyrazolone-4'-sulfonic acid, 1-(6'-chloro)- phenyl-3-methyl-5-pyrazolone-3'-sulfonic acid, 1 (2'- methyl)-phenyl-3-methyl-5-pyrazolone-4'-sulfonic acid, 1-

phenyl-3-methyl-5-pyrazolone 3 carboxylic acid, 1- phenyl--pyrazolone-3-carboxylic acid and l-hydroxy-4- methylbenzene.

The coupling of the aminodisazo dyestuffs (a) is carried out with the copper complex compounds of the monoazo dyestuffs (b) to yield the new polyazo dyestuffs, and this is advantageously effected in the presence of an organic base, such as pyridine, quinoline, etc. at temperatures of 0 to 60 C.

The new polyazo dyestuffs are advantageously treatedfor being converted into the copper complex compounds in substance-with copper-yielding agents in such manner that the methoxy groups are split. This may be effected according to various methods known from the literature, for example by heating with copper salts in weakly acid to alkaline medium in the presence or absence of ammonia, organic bases, and optionally with the use of superatmospheric pressure, or in a fusion of alkali salts of low molecular weight aliphatic carboxylic acids.

SIO H Ross The new polyazo dyestuffs contain at least two sulfonic acid groups and correspond to the formula (Let stands for the radical of a hydroxynaphthalene-mono-, -dior -tri-sulfonic acid, or of a S-pyrazolone or S-pyrazolone sulfonic acid or of 1-hydroxy-4-methylbenzene, and x stands for H, CH3, OCH3 or NH.acyl, and wherein -azo'- is in para-position to -azo"-, and dye cotton and fibers or regenerated cellulose in gray to olive-green shades-of good fastness to light and to washing. After treatment of the dyeings with copper-yielding agents fur ther improves the fastness properties thereof.

The following examples set forth representative exemplary embodiments of the invention, and these examples are intended to be solely illustrative and not at all limitative. In these examples, the parts and percentages are by weight and the temperatures are expressed in degrees centigrade.

Example 1 56.7 parts of the aminodisazo compound-obtained by coupling diazotized 2-an1inonaphthalene-6,8-disulfonic acid With l-amino-S-methylbenzene, further diazotizing and coupling with 1-amino-2-methoxy-5-methylbenzeneare stirred into 500 parts of water, 7 parts of sodium nitrite added to the suspension, and the latter adjusted so that it is acid to Congo by the addition of 50 parts of concentrated hydrochloric acid and while stirring thor oughly at 10-12". The diazotization is complete in about two to three hours. The obtained diazo suspension is combined at room temperature (about -25") with a solution of 55.2 parts of the copper complex compound of the formula HOaS- SO:H

I on, Hots -N=N -so,n

and dyes cotton and fibers of regenerated cellulose in olive shades of outstanding fastness to light and very good fastness to washing.

Dyestufis with similar excellent properties are obtained when, while otherwise proceeding as aforedescribed in the present example, the initial component of the aminodisazo compound 2-aminonaphthalene-6,S-disulfonic acid-is replaced by 2-aminonaphthalene-3,6-disulfonic acid, 2-aminonaphthalene-4,8-disulfonic acid, Z-aminonaphthalene-S,7-disulfonic acid, l-aminonaphthalene-3,6-disulfonic acid, 1-aminonaphthalene-3,8-disulfonic acid, 1-arninonaphthalene-4,8-disulfonic acid, 1-aminonaphthalene-4-sulfonic acid, l-aminonaphthalene-5-sulfonic acid,

1-aminonaphthalene-6-sulfonic acid,

1-aminonaphthalene-7-sulfonic acid, 1-aminonaphthalene-8-sulfonic acid, Z-aminonaphthalene-l-sulfonic acid, 2-aminonaphthalene-5-sulfonic acid, 2-aminonaphthalene6-sulfonic acid, Z-aminonaphthalene-8-sulfonic acid, 1-aminobenzene-2,4-disulfonic acid, l-aminobenzene-2,S-disulfonic acid, 1-aminobenzene-2-sulfonic acid, 1-aminobenzene-3sulfonic acid, 1-aminobenzene-4-sulfonic acid, 1-amino-2-methylbenZene-4-sulfonic acid, 1-amino-2-methylbenzene-5-sulfonic acid, l-amino2,4-dimethylbenzene-6-sulfonic acid, 1-arnino-3-carboxy-4-hydroxybenzene-5-sulfonic acid, Dehydrothio-p-toluidine-monosulfonic acid, or Dehydrothio-p-toluidine-disulfonic acid,

or when, while starting from any of the foregoing initial components, the middle component--l-amino-3-methylbenzene-of the aminodisazo compound is replaced by aminobenzene, or

l-amino-Z-methoxybenzene, 1-amino-2,S-dimethylbenzene, 1-amino-2,5-dimethoxybenzene, 1-amino-2,S-diethoxybenzene, l-amino-3-acetylaminobenzene, 1-amino-2-methoxy-5acetylaminobenzene, l-aminonaphthalene,

1-amino-2-methoxynaphthalene, or 1-amino-2-ethoxynaphthalene,

by 2 ,737,616 or when, in any one of the aforementioned combinaor when, starting from any of the foregoing inital conitions, the end component-1-amino-2-methoxy-5-methylponents, the middle component 1-aminonaphtha1ene-7- benzene-of the aminodisazo compound is replaced by sulfonic acid of the aminodisazo compound is replaced by 1-amino-naphthalene-6-sulfonic acid, or when, in any of the foregoing combinations, the 1-amino-2-rnethoxy-5- methylbenzeneend component in the aminodisazo compound is replaced by any one of the end components enumerated in Example 1, or when, in any of the foregoing combinations, the radical (Q) of the copper com plex compound (0) is replaced by one of the radicals enumerated inExarnple 1 r Example 3 1-amino-2-methoxybenzene, 1-amino-2-methoxy-5-acetylaminobenzene, l-amino-2-methoxy-5-propionylaminobenzene 1-amino-2-methoxy-5-formylaminobenzene, 1-amino-2-methoxy-5-benzoylaminobenzene, 1-amino-2-methoxy-S-carbethoxyaminobenzene, or 1-amino-2,5-dimethoxybenzene, or when, finally, in any one of the foregoing combinations, the copper complex compound (a) is replaced by f pp complex p wherein the radical (Q) 56.7 parts of the aminodisazo compound used in Exn3Placed y the l'adlcal 0f 15 ample l are coupled in the manner described in the said 1-hydroxynaphthalene-3-sulfonic acid, example, with Parts of the pp complex 1-hydroxynaphthalene-4-sulfonic acid, Pound of r 1-hydroxynaphthalene-S-sulfonic acid,

2-hydroxynaphthalene-6-sulfonic acid, or

2-hydroxynaphthalene-7-sulfonic acid. i /N Example 2 Ho,s- N- =\N -o 87.7 parts of the aminodisazo compoundobtained by H! coupling diazotized l-aminonaphthalene-7-sulfonic acid (R) with 1-aminonaphtha1ene-7-sulfonic acid, further diazotiz- H (d) ing and coupling with 1-amino-2-methoxy-5-methylbenzeneare diazotized after the manner described in Example 1. The obtained diazo compound is combined thus-obtained polyazo dyestuff corresponds to the formula with a solution of 55.2 parts of the copper complex comand dyes cotton and fibers of regenerated cellulose in pound (c), 600 parts of water and 1500 parts of pyridine. 40 olive shades of outstanding fastness to light and very After conversion of the resultant tetrakisazo dyestufi good fastness to washing.

into the copper complex compound, there is obtained a Dyestufis with similar properties are obtained when, dyestuff which corresponds to the formula in the preceding paragraph, the initial, middle and/or A0 11 SOaH and dyes cotton and fibers of regenerated cellulose in end component of the aminodisazo compound is replaced gray shades of outstanding fastness to light and good by one of the corresponding components enumerated in fastness to washing. Example 1, or when, in any of the resultant combinations,

Dyestuifs with similar properties are obtained when, the radical (R) of the copper complex compound (d) is rewhile otherwise proceeding as aforedescribed in the presplaced by the radical of v ent example, the starting component l-aminonaphthalene- 7-sulfonic acid in the aminodisazo compound is replaced by one of the initial components enumerated in Example 1 1-phenyl-3-methyl-5-pyrazolone-2'-sulfonic acid, 1-pheny1-3-methyl-5-pyrazolone-3'-sulfonic acid, 1-(6'-chloro)-phenyl-3-methyl 5 pyrazolone-3-sulfonic or by acid, l-amtnonaph 1-(2'-methyl)-phenyl-3-methyl 5 pyrazolone-4-sulfonic Z-ammonaphthalene, acid, A o 1-phenyl-3-methyl-5-pyrazolone-3-carboxylic acid, or

1-amino-3-methylbenzene, 1-amino-4-methylbenzene, 1-amino-2,5-dimethylbenzene, 1-amino-4-hydroxybenzene-3-carboxylic acid, 1-amino-4-hydroxy-5-methylbenzene-3-carboxylic acid, 1-aminobenzene-4-carboxylic acid, 1-amino-2-carboXybenzene-4-sulfonic acid, 1-amino-2-carboxybenzene-S-sulfonic acid, or 1-aminobenzene-2,S-dicarboxylic acid,

1-phenyl-5-pyrazolone-3-carboxylic acid.

Example 4 52.9 parts of the aminodisazo compoundobtained by coupling diazotized l amino 4 hydroxybenzene-3-carboxylic acid with 1-aminonaphthalene-7asulfonic acid, further diazotizing, and coupling with l-amino-Z-methoxy- 5-methylbenzene'are diazotized after the manner set and then subjected to demethylating coppering. The

8 forth in Example 1, coupled with 63.2 parts of the copper the radical (T) of the copper complex compound (e) is complex compound of the formula replaced by the radical of 0 l-hydroxynaphthalene-3,8-disulfonic acid, l 1-hydroxynaphthalene-4,8-disulfonic acid, 110:3 N= 2-hydroxynaphthalene-3,fi-disulfonic acid,

2-hydroxynaphthalene-6,8-disulfonic acid, or a a l-hydroxynaphthalene-3,6,8-trisulfonic acid.

H (T) (e) 7 Example 5 I and then subjected to demethylating eoppering. The thus- 1 part of a dyestufi prepared according to any of the obtained polyazo dyestufi corresponds to the formula foregoing Examples 1 to 4 is dissolved in 3000 parts of OC t1 0 $0011 $11: HO;S N=N HO-N=N- -N=N -1 I=N- Hots -so,H

I an 5 and dyes cotton and fibers of regenerated cellulose in gray Water, and 5 parts of Glaubers salt are added to the shades of outstanding fastness to light and very good fastsolution The thus-prepared dyebath is heated to 50 ness to washing. By aftcrtreating the dyeings with copper; 30 and, at this temperature, 100 parts of cotton are entered. yielding agents, the fastness to wet treatment can be The dyebath is then heated to 95 in the course of l520 further enhanced. minutes and maintained at this temperature for 15 minutes. Dyestufis with similar fastness properties are obtained Thereupon 5 to 15 more parts of Glaubers salt are added when, while otherwise proceeding as set forth in the and dyeing continued at 95 for about minutes more. present example, the initial component of the arnino- After cooling the bath to 50, the dyed material is withdisazo compound is replaced by drawn, rinsed thoroughly and dried. The resultant dyeing has outstanding fastness to light and good fastness to wet 1-amino-3-carboxy-4-hydroxybenzene-5-sulfonic acid, treatments, y Y- y b0Xylic acid, Having thus disclosed the invention, what is claimed is: l-aminobenzene-2-sulfonic acid, 1. A polyazo dyestufr" which contains at least two sull-aminobenzene-3-sulfonic acid, fonic acid groups and corresponds to the formula l-arninobenzene-4-sulfonic acid, l-amino 2,5-dirnethylbenzene-3-sulfonic acid, 1-aminonaphthalene-4-sulfonic acid, :0 Ho s- N= N-R 1-aminonaphthalene-5-sulfonic acid, 1-aminonaphthalene-6-sulfonic acid, -B- 0 1 l-aminonaphthalene-7-snlfonic acid, a) l A) 1-aminonaphthalene-8-sulfonic acid, l-amiflonflphthalene, wherein A stands for a member selected from the group 2"afniflfillapl'lthP116116, consisting of diazo component radicals of the benzene Aminobenzene, and naphthalene series, B stands for a member selected l-amino-4-rnethylbenzene, from the group consisting of middle component radicals 1-amino-2,S-dimethylbenzene, of the benzene and naphthalene series, l-aminooenzene-4-carboxylic acid, or Dehydrothio-p-toluidine-monosulfonic acid, or when, starting from any one of the foregoing cornbinations, the middle component of the aminodisazo compound is replaced by 1-aminonaphthalene-o-sulfonic acid, or, if

the initial component contains a solubilizing group, by sulfonic acids, of 5 pyraZo10neS and of l hydroxy 4 meth of the Puddle compcllems enuimefated Example ylbenzene, x stands for a member selected from the group 1, or when, in any one of the foregoing combinations, the consisting of hydrogen, CH QCH3 d NH end component of the aminodisazo compound is replaced d wherein -azostands in para-position to -azo"-.

by one of the end components enumerated in Example 1, 2. The polyazo dyestuif which corresponds to the foror when finally, in any one of the foregoing combinations, mula stands for a member selected from the group consisting of residues of hydroxy-naphthalene-mono-, -diand -tri- 2,737,610 v 10 3. The polyazo dyestufli which corresponds to the formula ()C}1 O on, Hogs N=N- SO3H 4. The polyazo dyestuif which corresponds to the formula 51.: The polyazo dyestufl which corresponds to the form References Cited in the file of this patent UNITED STATES PATENTS 2,242,456 Delfs May 20, 1941 2,640,824 Ischer June 2, 1953 2,673,200 Ruckstuhl et a1 Mar. 23, 1954 

1. A POLYAZO DYESTUFF WHICH CONTAINS AT LEAST TWO SULFONIC ACID GROUPS AND CORRESPONDS TO THE FORMULA 